DE2252759A1 - RESIN FIBERS, IN PARTICULAR FOR THE MANUFACTURE OF PAPER, AND METHOD FOR MANUFACTURING THE SAME - Google Patents

Description

Resin fibrils, especially for the production of paper, and methods of making the same

For this application, priority dated October 29, 1971 is derived from US patent application serial no. 193,987 claimed. - ■ -. ■ - ■ -

The invention relates to improved pibrils, which are particularly suitable for the production of paper, and to a method to manufacture the same. In particular, the invention relates to a method for incorporating fillers in Paper, by way of the incorporation of fillers into the fibrils from which the paper is made can be. The invention is particularly.an improved Process for the production of pibrils containing full substance from polymers, where the filler is made of the Polymerizaten produced fibrils is encapsulated. These pibrils containing full substance are particularly suitable as paper stock for processing in conventional paper machines.

Past all paper types contain inorganic fillers. There are papers that can contain inorganic fillers in amounts of up to 40 ^c / o of their basis weight. Fillers are added to these types of paper in order to improve the lightness, opacity, smoothness, the capacity for printing inks or ink and the hand of the paper

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reduce manufacturing costs. However, the fillers used in papermaking reduce the degree of sizing and often the strength of the sheet of paper.

In the manufacture of paper from wood pulp, the fillers are normally used in the formation of the fleece (sheet formation) added. The retention of these filler particles The paper often presents a problem for which a solution is still being sought. Apparently they are both hydrodynamic Mechanisms as well as colloidal aspects or the common flocculation for the retention of the filler particles between the cellulose or wood pulp fibers the formation of the paper sheet is essential.

Synthetic polymers in liquid form can be converted directly into solid fibrous products by various processes. Examples of "such methods are the conventional spinning of polymer solutions, polymer melts, plasticized polymer masses and reactive polymer formers through spinnerets with a plurality of spinning holes, spray gun methods in which a liquid polymer stream is refined by air or electrical fields, shear precipitation methods and others Preferred methods for the production of fibrous products on? Polymer solutions forms the subject of the patent (patent application dated the same filing date, entitled "Process for producing fibrils suitable for papermaking", S-471). Polymers of high molecular weight, which give the fibers advantageous physical properties, such as increased strength and flexibility, often cannot be pre-spun from conventional spinnerets because their melt and solution viscosities are often too high for spinning at pressures that are technically possible are. According to the spray gun method and similar methods, short, fine fibrils of random length and irregular shape are obtained at higher production rates: Longitudes and with less critical process restrictions old? in conventional spinning through spinnerets with many spinning holes. Fiber products made like this are for some, however

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"Suitable for limited textile applications; according to these methods is obtained, however, without further process training and controls do not contain fibrous products many different textile applications are suitable because the fibers do not have sufficient strength and uniformity for the manufacture of products of high quality.

In the last few years there has been a need in lechnik for better paper containing one or more types of synthetic fibilli. There are already several paper pulps from synthetic lasers and methods are known by which such paper can be produced. These known paper stocks have been successful for quite limited and special uses4 but since the The structure of the synthetic fibers contained in these paper stocks is quite dissimilar to the natural paper stock fibers are, these compositions of matter have in the great majority of cases in which a product is required that has the essential properties of the paper and also has some properties that are found in natural paper cannot be found, not proven.

You already have many different types of fibrous material « for the separation of fleece-like or paper-like products from aqueous dispersion according to the paper manufacturing technique used * Depending on the type of starting fiber material and the conditions under which the fibers are used in papermaking are treated, sheet-like products can be used obtained with different properties. This is how paper is made from cellulose fibers, and it is already many attempts have been made to create a similar, leaf-shaped Manufacture product from fully synthetic fibers.

By and large, the process for making paper or similar sheet-like products is independent the fibers used remain the same, but one has made a number of minor changes, such as' · e.g. the pretreatment of the fibers by grinding or refining or the incorporation of additives such as binders, Adhesives, thickeners, fillers and the like.

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The invention is based on the object of providing new, improved fibrils which are particularly suitable suitable for the production of paper in the paper machine.

The invention provides synthetic resin fibrils containing filler, in particular made from linear ethylene polyesters of high molecular weight, the significant amounts of fillers encapsulated in the synthetic resin that make up the pibrils, hold and are particularly suitable for the production of paper in conventional paper machines, as well as a process for their production to disposal.

The invention also relates to filler-containing paper with improved properties that is obtained from these pibrils can be produced.

The invention relates to a synthetic resin fibril, in particular for the production of paper, which is characterized in that it is made of a thermoplastic synthetic resin and a filler substantially encapsulated therein and a length of about 1 to 5 mm and a diameter of has about 10 to 30 μ. The invention further comprises a method for producing such pibrils and that from them Pibrils made paper. The pill is made of linear Very high molecular weight polyethylene containing about 5 to 50 weight percent fillers, which are essentially are encapsulated in the linear polyethylene that makes up the eyeglasses. The fillers can be organic or inorganic Substances are and should be used as solvents used hydrocarbons be insoluble.

It has been found that filled pibrils of good texture, which are particular for the production of Paper in conventional paper machines after conventional Process suitable, can easily be made from synthetic resins. It has also been found that virtually all filler particles encapsulated in the synthetic resin of the fibrils being formed. In particular, it was found that fibrils from a linear ethylene polymer of high molecular weight, especially a polymer with a high load

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Sehmelzindex (= Schraelzindex determined under high stress), determined according to ASTM test standard 21258-655 * Condition F, of less than -0.25 g / 10 min, can easily be provided with fillers that are insoluble in hydrocarbons, that the FüÜstoffteilchen are encapsulated in the synthetic resin fibrils.

The fillers incorporated into the fibrils can be inorganic or organic; the only requirement is that they must be insoluble in the solvent used to make the fibrils. Fillers that have been used in this sense include calcium carbonate, titanium dioxide, silicon dioxide, various types of clay, particularly kaolin, and pigments. All of these substances are fillers that are usually added to wood or cellulose pulp during paper production The fillers can be incorporated into the fibrils in various amounts from about 5 1/2 or less to about 50 $ , these percentages being based on the weight of the filler-containing fibrils. The paper produced from the fibrils then has the same high filler content without any loss of filler because practically all of the filler is encapsulated in the synthetic resin of the fibrils.

In order to produce the filler-containing fibrils according to the invention, the synthetic resin is first dissolved (often at elevated temperature) in a solvent consisting of hydrocarbons, especially high-boiling hydrocarbons, whereupon the fillers are suspended in finely divided form in the solution and then the end. the solution by erspin ~ -.? nen or by the method of the aforementioned patent (patent application from the same Anttieldetag) fibrils prepared. The preferred solvents for dissolving the polymer are aliphatic hydrocarbons with a boiling range from 135 to 225. Two examples of such solvents are the commercially available solvents "Apco 140" and "Speedfjol".

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A preferred method of making fibrils Polymer solutions are the subject of the above Patents (patent application filed on the same filing date, S-471), according to which the pibrils with the aid of the centrifugal spinning device described and illustrated there and according to the ones described there Process to be spun “Bio fillers can be added to the solvent before the addition of the polymer, at the same time with the addition of the polymer or after dissolving of the polymer is the only condition the ones that you have to produce before or during the solution spinning the pibrils are suspended and well distributed in the solution. If you work according to this procedure, you will succeed substantial amounts (well over 90 percent by weight, sometimes even 100 percent by weight) of the fillers used in the Encapsulate pibrils.

In the examples below, the parts and percentages relate to weight percent unless otherwise specified lots.

example 1

Fibrils containing filler are made from a polyethylene solution and silicon dioxide (SiO ₂ ); the silicon dioxide is used in an amount of about 50 percent by weight of the total solids added to the solution from which the pibrils are made. First, 7.5 g of linear ethylene polymer of high molecular weight are dissolved at 150 ° C. in 1500 ml of a solvent consisting of aliphatic hydrocarbons with a boiling range of 180 to 200 ° C.! The ethylene polymer has a pu . -Low high-load melt index that this size after.der ·. ASTM test standard D1238-65T, Condition P, cannot be determined. 7.5 g (50 percent by weight of the total amount of the pesticides added to the solvent) silicon dioxide produced by high-temperature pyrolysis (matting agent "Aerosil ST" from Degussa) is added to this solution. The silica is suspended in the solution with constant stirring, and the solution is then spun into fibers which

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have a good suitability for paper cutting and length from about 1 to 5 mm and diameters in the range from about Ms 30 µ. exhibit.

2 g of these polyethylene fibrils become 500 ml of water added containing 10 drops of surfactant ("Triton 100"). The slurry obtained in this way is fed to the pulp on a manual scoop paper machine according to Noble and Wood and diluted with 5 Raumteileii (2500 ml) of water for leaf formation. In the paper machine, a sheet of paper is made in the usual way made and then dried. It is found that the paper has good properties and is 30% by weight Contains silicon dioxide. ,

Example 2

Polyethylene fibrils are produced according to Example 1, but with calcium carbonate (OaCO ₃ , "Fisher GP" from Fisher Scientific Company) as filler in amounts of 20 percent by weight, based on the total amount of the solids added to the solvent. 30 g linear polyethylene of high molecular weight and a high load melt index, determined according to ASTM test standard D1238-65T, Condition F, of 0.24 g / 10 min v / earth at 150 0 in a made of aliphatic hydrocarbons with a boiling range of 155 up to 180 ° C existing solvent dissolved. 7.5 g of calcium carbonate are suspended in this solution. From the filler-containing polyethylene fibrils spun according to Example 1, paper with good properties is produced according to Example 1 and contains 18.6 percent by weight of calcium carbonate. This high filler content shows that far more than 90% of the calcium carbonate added to the polyethylene solution have passed into the polyethylene fibrils and the paper made from them. ■

Example 3

According to Example 1, fibrils and a sheet of paper, but with titanium dioxide (TiOp> "Zopaque" from Glidden Company) in an amount of 20 percent by weight, based on the dem

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Solvent-added total solidsBieiig «, produced. The same solvent and the same polymer are used in the same amounts as in Example 2. In 7> 5 g of titanium dioxide are added to the polyethylene solution while stirring suspended. By spinning from solution, as in the previous ones Examples, one obtains iron polyethylene fibrils of good quality for papermaking. A paper sheet produced therefrom according to Example 1 shows good Äigensohaften and has a titanium dioxide content of 19 »96 percent by weight, from which It turns out that almost all of the titanium dioxide is in the fibrils and has therefore passed into the paper.

Example 4

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The procedure of Example 1 is used with the same polyethylene and the same solvent in the same amounts as in Example 2. As a filler. trird in this Pail Kaolin ("Ultra-white 90" from Engelhard Minerals & Chemicals Corporation) in an amount of 9 percent by weight, based on the total amount of solids added to the solvent, applied. In a solution of 30 g of polyethylene in 1500 ml of solvent become 3 g of kaolin suspended. From the solution become, as in the preceding Examples, spun polyethylene fibrils containing filler, which are processed into paper according to Example 1 · Bas paper has good properties and a clay content of 6.2 percent by weight.

Example 5

The procedure of Example A is followed, but the filler used is calcium carbonate (CaCO ₅ "fisher CP" from Pisher Scientific Company) in an amount of 33 percent by weight, based on the total amount of solids added to the solvent. The same polymer and solvent are used in the same amounts as in Example 2. In the polyethylene solution prepared at 150 ° C., 15 g of calcium carbonate, which have been prewetted with 30 ml of mineral oil, are suspended with stirring. As in

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the previous examples, polyethylene fibers of good quality Quality spun »from which then according to. Example t a sheet of paper is made and dried «The paper has a good consistency and contains 28 percent by weight calcium carbonate.

Example 6

The procedure is as in Example 1, but used as a filler Kaolin ("MinChem Special Pulverized" from Engelhard Minerals & Chemicals Corporation) in an amount of 50 GSe Weight percent of the total solids added to the solvent amount of substance. To the “starting solution prepared at 150 ° 0 of 30 g of the linear polyethylene given in Example 2 in 15QÖ ml of the solvent specified in Example 2 30 g of kaolin were added, which were previously pre-wetted with 50 ml of mineral oil have been. The kaolin is suspended in the solution with stirring, and from the solution, as in the previous examples, suitable materials for paper production are obtained Polyethylene fibers are spun, which are then processed into paper according to Example 1. The sheet of paper shows after the Drying good properties and contains 44 percent by weight kaolin,

Example 7

The instructions in Example 6 are used, however with another kaolin ("Min Chem Special Predispersed" the Engelhard Minerals & Chemicals Corporation) in the same Quantitiesc The paper obtained in this way shows good after drying Properties and has a kaolin content of 39 percent by weight., · -. '

Example 8

Example 6 and 7 are used, but with a different kaolin. ("Klondyke Predispersed". From Engelhard Minerals & Chemicals Corporation) in the same amounts. The paper sheet obtained at the end of the process contains 48 percent by weight of kaolin and has good paper properties. From this it follows that far more than 95 ° / ° of the polyacrylene solution added

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ten clay in the fibrils and the paper made from them have been withheld.

Example 9

The procedure of Example 1 is followed, but with calcium carbonate (CaCO ,, "Atomite ¹¹ from Thompson, Weinman & Company) as filler in amounts of 20 percent by weight, based on the total amount of solids added to the solvent 10 g of the ethylene polymer given in Example 1 and 2.5 g of calcium carbonate are added simultaneously at 150 ° C. After the polymer has gone into solution, turn out of the solution in which the calcium carbonate is kept in suspension by boiling, as in The paper produced therefrom according to Example 1 shows good paper properties after drying and has a calcium carbonate content of 12.3 percent by weight.

The following two examples are used to compare the physical properties of paper made from filler-containing Fibrils or fibrils that do not contain filler, has been made. The paper produced according to the first of these examples has a kaolin content of 29? £, ■ while the paper made according to the second example contains no filler.

Example 10

According to the method of Example 1, fibrils are produced which contain kaolin ("Klonäyke Predispersed" from Engelhard Minerals & Chemicals Corporation) as filler in an amount of 40 percent by weight, based on the total amount of solids added to the solvent The specified solvent is dispersed at 150 ° C. 15 g of the ethylene polymer specified in Example 1 and 9.9 g of the above-mentioned kaolin at the same time. After the polymer has been dissolved in the solvent and the clay has been suspended, the Vex 'is driven out of the solution

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of Example 1 filled polyethylene fibrils he spönnen. The paper produced from these fibrils according to Example 1 has a clay content of 29% by weight after drying. - ·

s example

(Comparison example)

Polyethylene fibrils are produced according to Example 10, but without filler. Me fibrils show a good consistency for paper production and, as in Example 10, are processed into paper which, after drying, shows good paper properties. ; _:

Some physical properties of those according to Example 10 and 11 obtained paper sheets are compared in the table below. "

Property * Example 11 Example 10

Basis weight, g / πκ Pick, mm

Apparent density, g / cm tensile strength, kg / 15 mm

Tear length, m -

Elongation at break, Elmendorf tensile strength, g / sheet Elniendorf tear factor, Mullen burst strength, g / cm Mullen burst factor MIT pallet strength

Flat weight, g / m folds up to the break Foldings to break, area breaking stress, kg -

* Determined according to the Tappi-lvTorm regulation Ko. T22Q.

71.25 67.57 0.206 0.183 0.346 0.369 , 1.62 1.44 1515.8 ■ 1420.7 8.11 11.37 173.3 108.6 243.2 160 ^ 7 ' 1308 1076 18.36 . 15.92 69.38 73.32 - 315 589. 9-1443 9-4004 0.76 0.79

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As the table shows, most of the physical properties are well preserved when moving from the paper containing no filler (Example 11) to the paper containing filler (Example 10).

Besides the observation that ii »pibrils consist of linear High molecular weight polyethylene readily in hydrocarbons allow insoluble fillers to be incorporated, has it been found that? most of the filler particles from the Fibrils are encapsulated. As a result of this type of encapsulation, the filler particles are obtained from the fibrils Paper with significantly improved resistance to abrasion, scuffing and cracking. The fact that the filler particles in The fibrils themselves are encapsulated can be determined by experimentation show where according to Example 5 made of polyethylene fibrils of high molecular weight, which is called calcium carbonate Containing filler, manufactured paper is immersed in hydrochloric acid, which contains a wetting agent. Hit the immersion Only a few bubbles of carbon dioxide will slowly develop. If you use the same polyethylene using the same process Produces filler-free fibrils, the calcium carbonate in powder form to the fibril slurry in papermaking adds and the paper produced in this way in a salic acid solution immersed, which contains a stimulant, one notices a strong bubbling due to the production of carbon dioxide, As a result, the calcium carbonate of this paper is exposed to the action of hydrochloric acid. It follows, -that when working according to the inventive method the Filler particles are almost completely encapsulated by the polyethylene fibrils themselves.

This type of incorporation of fillers into the Fibrils themselves make it possible to incorporate fillers into the paper made from the fibrils, without glue, resinous Use retention aids or other similar additives commonly used in papermaking be used. This type of storage of fillers not only represents savings, but also makes it easier Pollution problems that are currently being caused by the sewage the paper industry.

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The selection of the fillers that can be used according to the invention is not limited to the above substances; one can Use inorganic and organic substances, provided they are only insoluble in the solvent used during manufacture are. Furthermore, the method according to the invention can also be used to store pigments in synthetic resin fibrils. Such pigments can be used to make white or colored paper of high degree of opacity and exceptional Establish tear resistance.

Another important benefit of the bulking Resin paper stock versus non-fibrous synthetic resin paper stock is that with. raw material costs can be saved in papermaking. By adding substantial Amounts of filler to the polyethylene fibrils, in particular by adding; large amounts of the above inorganic Fabrics, "are made up of the cost of papermaking Another benefit is significantly lower in polyethylene in that you get polyethylene fibrils by adding fillers with a specific gravity of more than 1, which is beneficial when the fibrils are from aqueous suspension to be processed into paper; because the density influences the behavior of the fibrils in aqueous dispersions, and if the fibrils are to behave similarly to cellulosic fibers, they must have densities greater than 1. ■ - - -.- ■■■. .

The fibrils produced according to the invention can be used in any proportions with fibrils of other origin, how to be mixed with untreated or treated synthetic fibers or with natural cellulose or wood pulp fibers »by varying the proportions of these Different types of fiber can be used to produce paper types with very different properties, which, according to V / Un, more textile material or more paper-like.

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Claims (10)

Gulf Research & Development Company S-474 claims 1. Synthetic resin fibrils, especially for the production of paper, characterized in that it is composed of a thermoplastic synthetic resin and one substantially encapsulated therein Consists of filler and a length of about 1 to 5 mm as well has a diameter of about 10 to 30 μ. 2. synthetic resin fibrils according to claim 1, characterized in that that the thermoplastic resin is linear polyethylene of high molecular weight and the filler is insoluble in hydrocarbons. 3. synthetic resin fibril according to claim 2, characterized in that the polyethylene has a high-load melt index, determined according to ASTM test standard D1238-65T, Condition P, from less than 0.25 g / 10 min and the filler is an inorganic one Fabric is. 4. Kunstharzfi glasses according to claim 3, characterized gejjppu & se lehnet, that the inorganic filler in the fibril in quantities from about 5 to 50 pounds based on the weight ler fills off-containing fi goggles * are included. 5. Kunstharzfibrille according to claim 4, characterized in that the inorganic filler is calcium carbonate, titanium dioxide, silica, kaolin, or a coloring pigment is · - 14 - 309818/1157 S-474 foV ■ 6. Process for the production of filler-containing polyethylene fibrils according to claim 1 and 2, characterized in that a linear ethylene polymer of high molecular weight at elevated temperatures in high-boiling sites. Hydrocarbons dissolves, fine! filler particles are dispersed in the solution, which are insoluble in the hydrocarbons, the solution spun into fibrils and the bulking fibrils are washed and refined. 7c method according to claim 6, characterized in that an ethylene polymer with a high-load melt index, determined according to ASTM test standard D1238-65T, Condition F, used at less than 0.25 g / 10 min. 8. The method according to claim '7 », characterized in that calcium carbonate, titanium dioxide, silicon dioxide, kaolin or coloring pigments are used as fillers. 9. The method according to claim 8, characterized in that the filler is suspended in the solution in amounts of up to 50 percent by weight, based on the solids added to the hydrocarbons, and fibrils are produced which contain the filler in amounts of up to 50% of their total weight . "" ■ · ■ " 10. The method according to claim 6 to 9, characterized in that that the fillers in amounts of at least 5 percent by weight, based on the added to the hydrocarbons Solids, adds. - - 15 - 309818/1157 ORIGINAL INSPECTED